CN1003588B - Process for producing acylated diketone compound - Google Patents

Process for producing acylated diketone compound Download PDF

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CN1003588B
CN1003588B CN85109777.4A CN85109777A CN1003588B CN 1003588 B CN1003588 B CN 1003588B CN 85109777 A CN85109777 A CN 85109777A CN 1003588 B CN1003588 B CN 1003588B
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alkyl
cyanide
enol ester
production method
mole
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CN85109777A (en
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詹姆斯·布里安·黑瑟
帕米拉·戴尼斯·米拉诺
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Stauffer Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring

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Abstract

Rearranging the corresponding enol ester in the presence of a cyanide source to produce an acylated dione compound. In one embodiment, a cyanide source and a molar excess of moderately strong base relative to the enol ester are used. In another embodiment, the cyanide source is a stoichiometric amount of potassium cyanide or lithium cyanide relative to the enol ester, and a catalytic amount of a crown ether is used.

Description

The preparation method of compound of diketone acylate
The present invention is by making corresponding enol ester reset the method for preparing compound of diketone acylate.
Below said compound of diketone acylate class to have a chemical general formula as follows:
Wherein R is a group, will provide definition (generally can be aromatic series or aliphatics) below.Such compound was described in many piece of writing documents, and it has many purposes, for example, and as chemical intermediate and/or agricultural chemicals.The rest part of this molecular formula comprises the diketo part, generally has ring texture.The most available diketo includes 5～6 yuan of carbocyclic rings.The general structure of such compound of diketone acylate is:
Figure 85109777_IMG5
Wherein R is as indicated above, and n is 2 or 3.Its ring can 1 or more on the multi-position by or do not replaced by (as alkyl, aryl, alkylene etc.) group.
A kind of method of preparation compound of diketone acylate is disclosed by an european patent application, and publication number is No. 90262.This method is the hydroresorcinol and the reaction of substituted benzoyl cyanide that can be optionally substituted, and this reaction is to carry out in the presence of zinc chloride and triethylamine.This reaction has the some shortcomings part: benzoyl cyanide is a kind of somewhat expensive reagent, and one mole of diketone acylate of every production just produces about one mole of prussic acid.Therefore in this reaction, use more cheap, more facile acylating agent, and do not produce so that a large amount of prussic acid is desired.For example, Benzoyl chloride is exactly a kind of more cheap, available acylating agent; simultaneously, Benzoyl chloride is the acylating agent stronger than benzoyl cyanide, and in the presence of common catalyzer not with two carbonyl intermediary carbon atom acidylates; and one of them carbonyl of directtissima forms enol ester:
Can learn that from many reference acidylate cyclic diketones compound can be prepared by corresponding enol ester with the method for resetting:
Figure 85109777_IMG7
These documents disclose several dissimilar diketone acylates and enol ester are reset various catalyzer or the promotor for preparing diketone acylate.
For example, in " synthesizing " the 925th～927 page (1978), A Kehaimu people such as (Akhrem) has announced by hydroresorcinol and acylating agent (particularly acyl halide) reaction, the multiple acidylate cyclohexanedione product of two-step approach preparation.Wherein the first step is that acyl halide and cyclohexanedione react the generation enol ester in the presence of pyridine, changes then under the excessive 2 moles condition of aluminum chloride, resets and generates the acidylate cyclohexanedione.The molecular formula of the acylating agent that uses in this reaction is RCOCI, and wherein R is the phenmethyl of various alkyl (for example methyl, ethyl, propyl group), phenyl, substituted-phenyl, phenmethyl and replacement.
People such as " chemical file " the 53rd page of (1982) Turner uncle grade has announced by pyrone and alkyl or alkene fundamental mode acyl halide acylation reaction generates 3-acyl group-4-hydroxyl-2-pyrone and use the 4-dimethylamino pyridine of catalytic amount that the enol ester of generation is reset.
European patent application (publication number) the 123001st has announced that other aminopyrazole derivatives and some N-alkyl imidazole derivative are enol ester to be reset generated to have the suitable catalyst of the substituent acidylate cyclohexanedione of 5-carbonyl acid ester.
Russian patent has been announced at 160～170 ℃ for No. 784195, enol ester is reset generated 2-oleoyl-hexanaphthene-1,3-diketone.European patent application discloses to disclose for No. 80301 and make 5-(multi-methyl benzene base in the presence of lewis acid)-enol ester of hydroresorcinol resets the method that generates corresponding acidylate cyclohexanedione.Employed acylating agent comprises that acid anhydride and its molecular formula are the acyl halide of RCOCI, and wherein R is alkyl, fluoro-alkyl, alkenyl, alkynyl or phenyl.
The present invention is by in the presence of prussiate enol ester being reset to prepare the method for acidylate cyclic diketones compound.
The present invention is by enol ester being reset prepare the method for compound of diketone acylate, and its total reaction is:
Wherein rearrangement reaction is to carry out in the presence of prussiate.
Or rather, rearrangement reaction is carried out under following a kind of condition:
(a) prussiate of catalytic amount and concerning enol ester excessive 1 mole middle highly basic, as tertiary amine, alkaline carbonate or alkali metal phosphate; Or
(b) concerning enol ester, the cyclic crown ether of stoichiometric potassium cyanide or lithium cyanide and catalytic amount or similar acyclic crown ether.
The molecular formula of the resultant of this reaction is as follows:
Wherein R can be various alkyl, alkenyl, aryl (for example phenyl or substituted-phenyl), benzene alkyl (phenmethyl that can be optionally substituted, styroyl etc.), or other substituting group, substituting group as mentioned above.
The rest part of this molecular formula has an atomchain that connects the carbon atom of two carbonyls, so this diketone is a ring compound.Best diketone is an isocyclic compound, preferred diketone is cyclopentanedione and cyclohexanedione, can be replaced by alkyl, aryl or other substituted radical on one or more position of its ring, most preferably can be by any hydroresorcinol that replaces of one or more alkyl.
A compounds of especially preferentially selecting for use is: diketone is a cyclohexanedione, is can substituted benzoyl part by the acidylate group.In other words, R is substituted phenyl.In general, the molecular formula of this compound is:
Figure 85109777_IMG10
R wherein 1, R 2, R 3, R 4, R 5And R 6Be respectively hydrogen or C 1-C 6Alkyl (C particularly 1-C 4Or R alkyl), 1, R 2And R 3Be RaOC-, wherein Ra is C 1-C 4Alkyl, the phenyl that can be replaced arbitrarily by 2-5 methyl; Perhaps R wherein 1And R 2, or R 3And R 4, form C together 3-C 6Alkylidene group; (this compound has spirane structure); R 7Be halogen (chlorine, bromine, iodine or fluorine); Cyano group; C 1-C 4Alkyl; C 1-C 4Haloalkyl; Trifluoromethyl RkS(O particularly) n, wherein R kBe C 1-C 4Alkane alkyl, n preferably 0,1 or 2; C 1-C 4Alkoxyl group (particularly methoxyl group) or nitro; R 8, R 9And R 10Be respectively hydrogen or halogen-containing substituting group; C 1-C 4Alkyl; C 1-C 4Alkoxyl group, trifluoromethoxy, cyano group; Nitro; C 1-C 4Haloalkyl; C 1-C 4Alkylthio; Phenoxy group; Or substituted phenoxy group, wherein substituting group is that halogen or halogenated methyl or the two have both at the same time; RbS(O) n, wherein n is 0,1 or 2, Rb is C 1-C 4Alkyl, C 1-C 4Haloalkyl, phenyl or benzyl, , wherein Rc is C 1-C 4Alkyl;-NRdRe, wherein Rd and Re are respectively hydrogen or C 1-C 4Alkyl; RfC(O)-wherein Rf is a hydrogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl or C 1-C 4Alkoxyl group; SO 2NRgRh, wherein Rg and Rh are respectively hydrogen or C 1-C 4Alkyl; Or R 8And R 9With coupled, two adjacent carbonss on the phenyl ring constitute ring texture together.
Such compound (in its hexamethylene ring or phenyl ring arbitrary or two on have various substituting groups) open in following document: european patent application; No. the 90262nd, publication number; Following undecided fixed U.S. Patent application (being William J Mi Xieer people's such as (WilliamJMichaely) application) has transferred transferee's (being this application people), denomination of invention is: " a kind of 2-(2-substituted benzene formyl)-1; hydroresorcinol ", sequence number is 634408, applies on July 31st, 1984; Sequence number 640791 was applied on August 17th, 1984; Sequence number 752702 was applied on July 8th, 1985; Sequence number 722593 was applied on September 5th, 1985.The following U.S. Patent application that has transferred transferee (applicant cited below), file an application on December 20th, 1984, sequence number is 683900, denomination of invention be " a kind of 2(2-oil of mirbane formyl)-1; hydroresorcinol ", the applicant is Charlie Si G Ka Te (CharlesGCarter); Sequence number is 683899, denomination of invention be " a kind of 2-(2 '-cyano group benzoyl)-1; hydroresorcinol ", the applicant is Charlie Si G Ka Te, sequence number is 683898, denomination of invention is " a kind of 2-(2 '-substituted benzoyl)-hydroresorcinol ", and the applicant is Charlie Si G card top grade people; Sequence number is 683884; denomination of invention be " a kind of 2-(2 '-alkylbenzene formyl radical)-1; hydroresorcinol "; the applicant is Charlie Si G Ka Te (all these is the application about the weedkiller compound); Japanese patent application, publication number are 51/13750 and 51/13755, and the applicant is Japanese soda KK; these applications disclose some such compounds, as herbicidal intermediate.The disclosure of these documents is incorporated the present invention at this.
Other compound that can produce in this way is disclosed in the following pendent U.S. Patent application (common transfer): sequence number is No. 764110, on August 26th, 1985 is by David L, people such as (David L.Lee) Lee application, denomination of invention is " a kind of 2-(2-substituted benzene ethanoyl)-hydroresorcinol "; Sequence number is on December 20th, 683883,1984 by people such as David Lee L application, and title is " a kind of 2-(2 '-substituted benzoyl)-hydroresorcinol ", and disclosed compound is to mention under the title of " background technology and prior art " in the document.
Rearrangement of the present invention is to carry out in the presence of prussiate." prussiate " this speech is meant under rearrangement condition, forms or generation hydrocyanation and/or cyanide anion ionic material.Two kinds of embodiments are arranged.
In a kind of scheme, this method is to carry out in the presence of the excessive one mole middle alkaline at the cyanide anion ion of catalytic amount and/or prussic acid and concerning enol ester.
Prussiate is an alkali metal cyanide preferably, as sodium cyanide and potassium cyanide; The cyanalcohol that the methyl alkyl ketone of 1～4 carbon atom is arranged in alkyl is as acetone or methyl iso-butyl ketone (MIBK) cyanogen ketone; The cyanalcohol of benzoyl or C 2-C 5The cyanalcohol of fatty aldehyde (as acetaldehyde, propionic aldehyde etc.), zinc cyanide; Three (low alkyl) silyl prussiate, particularly trimethylsilyl cyanide, and prussic acid.It is a lot of that prussic acid is considered to advantage, because it can make speed of response fast and price is inexpensive, both available gaseous state, available again liquid state.When using gaseous state, can buy or produce on the spot in supplier's hand with metal cyanides and acid-respons.Reasonable prussiate is an acetone cyanohydrin in cyanalcohol.
In this embodiment, the consumption of prussiate can reach about 50 moles of % based on enol ester.Can under 40 ℃ of temperature, just can reach suitable speed of response during small-scale production with few amount to about 1 mole of %.The a large amount of a little catalyzer of extensive reaction, about 2 moles of %, then repeatability is better.The prussiate of general best 1～10 mole of %.
In this embodiment, this method is to carry out under middle highly basic condition excessive 1 mole concerning enol ester.Here " middle highly basic " this speech is meant the material that works as alkali, but its intensity and active between highly basic, as oxyhydroxide (can cause the hydrolysis of enol ester) and weak base.Between supercarbonate (can not work effectively).Middle weak base applicable to this scheme comprises organic bases, as tertiary amine and mineral alkali, as alkaline carbonate and phosphoric acid salt.Tertiary amine applicatory comprises trialkylamine, and as triethylamine, three alkyl group amine are as thanomin and pyridine.Mineral alkali applicatory comprises salt of wormwood and sodium phosphate.
The consumption of this alkali is about 1～4 mole of every mole of enol ester, preferably about 2 moles.
When prussiate is alkali metal cyanide, particularly during potassium cyanide, can adopt phase-transfer catalyst in the reaction.The phase-transfer catalyst of particularly suitable is a crown ether.
Character according to chloride of acid or acidylate product can be used multiple different solvent in the method.This reaction in preferably solvent be 1, the 2-ethylene dichloride.Other adoptable solvent depends on reactant or resultant, comprises toluene, acetonitrile, acetate dichloromethane ethyl ester, the different J base of dimethyl formamide and methyl ketone (MIBK).
In general, can under up to 80 ℃ of temperature, carry out according to the character rearrangement reaction of reactant and prussiate.In some cases, for example when having excessive by product and generate (for example when using neighbour-cyano group benzoyl halogen and alkali metal cyanide or acetone cyanohydrin) rearrangement as prussiate temperature is the highest should be no more than about 40 ℃.
Second kind of scheme of the inventive method be with potassium cyanide or lithium as prussiate, but its consumption is a stoichiometric quantity to enol ester, and no longer uses other alkali.Prussiate is that the phase-transfer catalyst with catalytic amount uses, and phase-transfer catalyst is crown ether or its no ring analogues.
In this scheme preferably prussiate be potassium cyanide.Crown ether is a hexaoxacyclooctadecane-6-6 preferably.Other hexadentate ligand compound, as cyclohexyl-hexaoxacyclooctadecane-6-6, dibenzo-18-crown-6 (DB18C6), and acyclic compound also are suitable for as five ethylidene glycol dimethyl ethers.
What lithium cyanide was suitable for is 16-crown ether-5.
In this scheme, independent alkali is unwanted, does not use here.
This scheme is applicable to the compound of producing general type, but is favourable when taking than the demulcent condition, so that when reducing the generation of by product, this scheme particularly suitable.For example prepare and on phenyl ring, have the substituent benzoylation cyclohexanedione of neighbour-cyano group.Present method can at room temperature be carried out, and can use the solvent similar to the first string, is preferably acetonitrile.
These two schemes all can use enol ester as raw material, perhaps produce this ester at the scene, for example produce with acylating agent and diketone.Enol ester one speech used herein is meant the enol ester of carboxylic acid.
When using enol ester as raw material in two schemes of the present invention, it can adopt any the producing in the currently known methods, comprises that usefulness (for example) acyl halide is to the dione compounds acidylate.
According to the present invention, can under the separation that is with or without the intermediate enol ester, carry out smoothly with acylating agent and diketone (acyl halide for example is as substituted benzoyl halogen, with diketone, as cyclohexanedione) preparation diketone acylate.When preparing with two-step approach, acyl halide or other acylating agent and diketone react in the presence of middle highly basic (as triethylamine).Enol ester can be separated from the product mixture that generates with known technology, as the solution that generates with bronsted lowry acids and bases bronsted lowry and saturated nacl aqueous solution cleaning, and dry.Go on foot-make enol ester and reset when generating diketone acylate and adopt different solvents better when second, this technology is useful.Exsiccant enol ester and suitable solvent (as acetonitrile or 1, the 2-ethylene dichloride) can be mixed then, and with an amount of prussiate and middle highly basic or crown ether in any contact.(according to selected scheme) prepares final product under suitable temperature.
Another kind of way can remain on enol ester in the reactant, can carry out the second step reaction (using identical solvent) by by add prussiate and additional alkali (as needing) in scheme.To produce diketone acylate.
In another approach; diketone acylate can be made by single stage method; even acyl halide or other acylating agent and diketone obtain enol ester at an amount of prussiate and an amount of middle highly basic or reacting down of crown ether (determining according to the scheme of selecting),, directly generate diketone acylate with its rearrangement.
Productive rate in the resulting separation that does not have enol ester is more or less the same.
Obtaining the diketone acylate product by reaction in the scheme of describing at first exists with the form of salt.Needed diketone acylate can obtain with the proper catalyst acidifying with suitable solvent extraction (if required), and in some cases, but this product reason acyl halide causes the existence of a small amount of carboxylic acid and be impure.The acidifying product solution can be contacted this sour salt of generation with sodium hydroxide dilute aqueous soln or other alkali that is fit to and remove this by product.In second scheme, can directly obtain diketone acylate product itself.
Following embodiment has illustrated the enforcement of the inventive method.
Embodiment 1: the rearrangement of enol ester
Carrying out a series of tests adopts multiple prussiate and solvent that corresponding enol ester is reset, preparation 2-(2 ', 3 ', 4 '-trichlorobenzene formyl)-1, the total process of hydroresorcinol is as follows: restrain (0.0094 mole) enol esters (with 2 with 3.0,3,4-trichloro-benzoyl chloride and 1, hydroresorcinol reacts in the presence of triethylamine and isolating method is produced) be dissolved in the 10ml indication solvent, and add the indication catalyzer of 10 moles of % and the triethylamine of 140 moles of % (calculating their amount according to enol ester).Mixture was reacted 4～18 hours at ambient temperature.With the reaction mixture dilute with water, distillation under reduced pressure removes and desolvates then.Slowly add 6N hydrochloric acid under stirring, make the aqueous mixture souring agent pH value of generation be about 1.Collect and filter the solid that obtains, under 75 ℃, be dried to constant weight.
The productive rate of the thick product of diketone acylate (material purity is not revised) is shown in Table 1.
Embodiment 2: the preparation of the isolating diketone acylate of no enol ester
The explanation of this example acyl halide and diketone, single stage method prepares diketone acylate by single stage method under the isolating situation of no intermediate enol ester.Its technology is as follows:
In flask, put into the 3.0g(0.027 mole) hydroresorcinol, 15 milliliters of indications solvents and 10 moles of %(centering mesosome enol esters) sodium cyanide.Reaction mixture is covered with nitrogen and keep at room temperature.Then, add the triethylamine (for enol ester) of 300 moles of %, will keep at room temperature by mixture.In mixture, add 100 moles of %(then to diketone) 2,3, the 4-trichloro-benzoyl chloride.Mixture is kept reacting at ambient temperature about 24 hours.Method recovery product by example 1 obtains 8.4 gram thick products (theoretical yield 93.2%, the purity unmodified of raw material).
Embodiment 3-6
Carry out a series of tests according to embodiment 2 similar methods, but use different catalyzer and solvent.Use identical reactant.All catalyst consumption are 10 moles of % based on the enol ester intermediate, and table 2 has provided these result of experiment, and its output is the purity unmodified of initial feed.
Embodiment 7
This example has also illustrated does not have the isolating production method of intermediate enol ester.
In a flask, put into 15 gram (0.13 mole) hydroresorcinols, 75 milliliter 1,2-ethylene dichloride and 0.24 milliliter of (based on 2 moles of % of enol ester) acetone cyanohydrin.These materials cover with nitrogen and flask are put into ice bath.
Then, add 54.36 milliliters of (34.96 grams, 0.39 mole) triethylamines and 32.86 grams (0.13 mole) continuously and be dissolved in 125 milliliter 1,2,3 of 2-ethylene dichloride, 4-trichloro-benzoyl chloride.When adding amine and Benzoyl chloride, the temperature of reaction mixture is raised to 40 ℃ and allow its reaction 2 hours.With the high pressure liquid chromatography monitoring, the area percent that demonstrates desired product was 84.6% when finishing in 2 hours, and all the other major parts are unreacted cyclohexanediones.
Then, the reaction mixture cooling and with 100 ml waters it is diluted.Add 3M sulfuric acid again, the pH value is transferred to 2.8 from 9.8, add 100 milliliter 1 simultaneously, the 2-ethylene dichloride dissolves the solid that begins to separate out once more.Mixture is divided into water and organic phase.The pH value of water layer (about 200 milliliters) is 2.6.
Water flushing organic phase and be separated once more (the pH value of water is 4).Then, wash organic phase at twice, all be separated once more after each flushing with the aqueous sodium hydroxide solution of 2.5N.The pH value of water is respectively 10.7,12.8.Again with 100 milliliters water flushing organic phase.
With its acidifying, make the sulfuric acid that is incorporated into from resulting all waters of above-mentioned separating step together and uses 3M the pH value be reduced to 2.1.The blended water is put into ice bath and is kept at low temperatures.With filtering method precipitated solid in the solution is collected, in vacuum drying oven, solid drying is arrived constant weight.Obtain 39.19 grams like this.Fusing point is 150～151 ℃ a desired product.By the high-pressure liquid phase chromatographic analysis and with the structure of relatively having determined product of known sample.
The production of embodiment 8:2-propionyl-hydroresorcinol
In the mixture of 3.0 gram (0.027 mole) hydroresorcinols that are dissolved in 15 milliliters of ethylene dichloride and 3.8 milliliters of (0.027 mole) triethylamines, in room-temperature water bath, drip the propionyl chloride of 2.3 milliliters (0.027 moles) under stirring and the cooling.At room temperature after about 4 hours of the continuously stirring, add the triethylamine of 7.5 milliliters (0.054 moles) and the acetone cyanohydrin of 0.25 milliliter (with respect to 10 molecular fractions of enol ester).In room temperature mixture is stirred one all night, dilute with water is also used the hcl acidifying of 6N then.The isolate phase is used the dichloromethane extraction water.The organic phase that merges makes to obtain the thick product of 4.68 gram solid-liquid blended with anhydrous sodium sulfate drying and concentrating under reduced pressure.Thick product is dissolved in methylene dichloride and uses the sodium hydroxide solution of 2.5N to extract, water extraction then.The water that merges is with the hcl acidifying of 6N and use dichloromethane extraction.Organic extract is with anhydrous sodium sulfate drying and concentrating under reduced pressure, obtains the oily products (theoretical value 84%) of 3.83 grams.Product structure can be determined by infrared, nucleus magnetic resonance and measuring method of mass spectrum.
Embodiment 9 and 10
These examples have illustrated the U.S. Patent application the 683rd in application on December 20th, 1984 by Charlie Si G Ka Te (Chacles GCavtez), the production method of the compound described in No. 900, the denomination of invention of this application is " a kind of 2-(2-oil of mirbane formyl)-hydroresorcinol ".
Embodiment 9:2-(2 '-oil of mirbane formyl)-hydroresorcinol
　　　　　　　
Figure 85109777_IMG12
2-nitrobenzoyl chloride (5.0 grams, 0.027 mole) and cyclohexanedione (3.0 grams, 0.027 mole) are dissolved in the methylene dichloride.Triethylamine (4.9 milliliters, 0.035 mole) added dropwise and with gained solution stirring 1 hour.With 2N hydrochloric acid (2NHQ), water, 5% solution of potassium carbonate and saturated nacl aqueous solution solution is washed, with anhydrous magnesium sulfate (MgSO 4) dry and concentrated under vacuum.Residuum is dissolved in 20 milliliters of acetonitriles.Add also stirred solution 1 hour at room temperature of triethylamine (1 equivalent) and potassium cyanide (40 moles of %).With after the ether dilution, extract with the 2NHCl flushing and with 5% solution of potassium carbonate.Aqueous extract is by acidifying and add ether.Filter the gained mixture and promptly draw 3.2 gram required compounds (fusing point is 132～135 ℃), identify by nucleus magnetic resonance, infrared and mass spectral method.
Embodiment 10:2-(2 '-oil of mirbane formyl)-5,5-dimethyl-hydroresorcinol
　　　　　
Figure 85109777_IMG13
Triethylamine (3.4 milliliters, 0.025 mole) is added drop-wise to 2-nitrobenzoyl chloride (3.5 grams, 0.019 mole) and 5, in the dichloromethane solution of 5-dimedone (2.4 grams, 0.019 mole).Stir after one hour under the room temperature, add 3 equivalent triethylamines and 0.4 milliliter of acetone cyanohydrin.With solution stirring 2.5 hours, then, extract with the 2NHCl flushing and with 5% solution of potassium carbonate.Extract with 2NHCl acidifying alkalescence extract and with ether.Ether moiety is used anhydrous MgSO with saturated and sodium chloride solution flushing 4Dry and concentrated under vacuum.Residuum recrystallize from ethyl acetate promptly obtains 2.0 gram required compounds (fusing point is 130～133 ℃), with nucleus magnetic resonance, infrared and mass spectrometry method it is identified.
Embodiment 11:2-(2 '-cyano group benzoyl)-4,4-dimethyl-hydroresorcinol
　　　　　　
This example has illustrated the production method of Charlie Si G Ka Te (CharlesGCarter) " certain 2-(2 '-cyano group benzoyl)-hydroresorcinol " by name compound described in No. the 683rd, 899, the U.S. Patent application of application on December 20th, 1984.
With 2-cyano group benzoyl chloride (3.9 grams, 0.024 mole) and 4,4-dimethyl-hydroresorcinol (3.3 grams, 0.024 mole) is dissolved in 75 milliliters of methylene dichloride.Drip triethylamine (5.0 milliliters, 0.036 mole) and at room temperature with gained solution stirring one and a half hours.Water, 2NHCl, 5% solution of potassium carbonate (5%K 2CO 3) and saturated nacl aqueous solution (salt solution) rinse solution, with anhydrous magnesium sulfate (MgSO 4).Dry and concentrated under vacuum.Residuum is dissolved in 20 milliliters of acetonitriles.Add triethylamine (4.4 milliliters, 0.032 mole) and acetone cyanohydrin (5) and with solution stirring two hours.With after the ether dilution, with the 2NHCl rinse solution and use 5%K 2CO 3Extraction.Aqueous extract extracts with the concentrated hydrochloric acid acidifying and with ether.Ether water and normal saline washing are used MgSO 4Dry and concentrated under vacuum.Residuum is purified with silica gel chromatography, obtains 1.2 gram viscous oils, identifies that with nucleus magnetic resonance, infrared and mass spectrometry it is a required compound.
Embodiment 12:2-(2 '-methyl thiobenzoyl)-4,4,6-trimethylammonium-hydroresorcinol
　　　　　　
Figure 85109777_IMG15
Present embodiment has illustrated Charlie Si G Ka Te people's such as (ChavlesGCavtez) U.S. Patent application (proposing simultaneously with above-mentioned application) the 683rd, the production method of by name " certain 2-(2 '-substituted benzene formyl)-hydroresorcinol " compound described in No. 898.
With 2-methyl thiobenzoyl chlorine (7.2 grams, 0.039 mole) and 4,4,6-3-methyl cyclohexanol diketone (5.0 grams, 0.039 mole) is dissolved in the methylene dichloride.Drip triethylamine (7.0 milliliters, 0.050 mole) and at room temperature with gained solution stirring one hour.With 2NHCl, 5%K 2CO 3And saline flush solution, use MgSO 4Dry and at vacuum concentration.Residuum is dissolved in 20 milliliters of acetonitriles.Add triethylamine (2.5 equivalent) and acetone cyanohydrin (0.4 milliliter) also at room temperature with solution stirring 45 minutes.With after the ether dilution, with the 2NHCl rinse solution and use 5%K 2CO 3Extraction.Aqueous extract extracts with hcl acidifying and with ether.The ether normal saline washing is used MgSO 4Dry and concentrated under vacuum.With the ether residuum of purifying, promptly obtain 5 gram viscous oils by development, identify that with nucleus magnetic resonance, infrared and mass spectrum (ms) assay method it is a required compound.
Embodiment 13:2-(4 '-bromo-2 '-three fluoro toluyls)-4,4 ', 6-trimethylammonium-hydroresorcinol
　　　　　　
Figure 85109777_IMG16
Present embodiment has illustrated the production method of Charlie Si G Ka Te (CharlesGCarter) " certain 2-(2-alkylbenzene formyl)-hydroresorcinol " by name compound described in No. the 673rd, 884, the U.S. Patent application of application on December 20th, 1984.
With 4-bromo-2-three fluoro methyl benzoyl chlorides (4.3 grams, 0.015 mole) and 4,4,6-trimethylammonium-hydroresorcinol (2.3 grams, 0.015 mole) is dissolved in 100 milliliters of methylene dichloride.With ice bath solution cooling and dropping are dissolved in 10 milliliters of triethylamines (2.1 milliliters, 0.015 mole) in the methylene dichloride.Then, removing cryostat also at room temperature stirred 30 minutes.With 2N hydrochloric acid (2NHCl), 5% solution of potassium carbonate (5%K 2CO 3) and saturated nacl aqueous solution (salt solution) rinse solution, with anhydrous magnesium sulfate (MgSO 4) dry and concentrated under vacuum.Residuum (5.1 gram) is dissolved in 20 milliliters of acetonitriles.Add also stirred solution two hours at room temperature of triethylamine (3.5 milliliters, 0.025 mole) and 0.4 milliliter of acetone cyanohydrin.Use drying tube (calcium sulfate) protection simultaneously.With after the ether dilution, with the 2NHCl rinse solution and use 5%K 2CO 3Extraction.Aqueous extract extracts with the concentrated hydrochloric acid acidifying and with ether.The ether normal saline washing, dry (MgSO 4) and under vacuum, concentrate.Gained oil is with silicagel column (80: 20: 1 ethane: ethyl acetate: acetic acid-elutriant), obtain 1.5 gram viscous oils, by nucleus magnetic resonance, infrared and mass spectrometry it is identified of purifying.
Embodiment 14:2-(4 '-chlorinated benzene formyl)-5,5-dimethyl-hydroresorcinol
Present embodiment has been explained the preparation method who makes cyanide source with prussic acid (sodium cyanide and vitriolic reaction gained).
With 5,5-dimethyl cyclohexane-1,3-diketone (7.01 grams, 0.05 mole) acetonitrile (80 milliliters) and Trimethylamine 99 (21 milliliters, 0.15 mole) are poured in the flask together and are put into nitrogen atmosphere.Add 4 dichlorobenzene formyl chlorides (6.4 milliliters, the 0.05 mole) solution that is dissolved in acetonitrile (20 milliliters) under in 15 minutes, stirring, in room-temperature water bath, cool off simultaneously.In being connected with another reaction flask of liquid level lower inlet duct, with sulfuric acid (0.25 gram, 0.0025 water (10 milliliters) solution mole), in 10 minutes under 85 ℃, add sodium cyanide (0.25 gram, 0.005 water (30 milliliters) solution mole) stirs simultaneously and makes nitrogen enter main reactor by the secondary response device at leisure.Then, the heating main reactor also stirs about two hours under 40 ℃, so reaction can be finished.
Carry out acidification with 60 ml waters lentamente with the reaction mixture dilution and with 40 milliliters of 6NHCl, product is precipitated out.Approximately stir after 5 minutes, collect solid phase prod with filter method, the water flushing, thereby and dry 11.85 grams (theoretical yield the 85.0%) beige solid that obtains, its fusing point is 134～134.5 ℃.
Embodiment 15:2-(4 '-chlorinated benzene formyl radical)-5,5-dimethyl-hydroresorcinol
Present embodiment has illustrated with three-low alkyl silyl prussiate makes the production method of cyanide source.
With 5,5-dimethyl cyclohexane-1,3-diketone (7.01 gram, 0.05 mole) acetonitrile (80 milliliters) and triethylamine (21 milliliters, 0.15 mole) are poured flask together into and are put into nitrogen atmosphere.In 15 minutes, stir 4-chlorinated benzene formyl chloride (6.4 milliliters, the 0.05 mole) solution that adding is dissolved in acetonitrile (20 milliliters), and cool off with the envrionment temperature water-bath.Add trimethyl silyl sodium cyanide (0.33 milliliter, 2.55 moles), and, in the time of 40 ℃, stirred 3 hours, so reaction is finished the temperature of reaction heating.
With reaction mixture dilution and with the acidifying of 40 milliliters of 6N hydrochloric acid solns, product is precipitated out with 160 ml waters.Approximately stir after 10 minutes, collect solid phase prod with filter method, and water dashes and dry, thereby obtain the beige solid of 13.2 grams (theoretical yield 95.0%), its fusing point is 135～134.5 ℃.
Embodiment 16:2-(2 '-cyano group benzoyl)-hydroresorcinol
Present embodiment has illustrated the production method of second scheme using stoichiometric potassium cyanide and crown ether.
In flask, pour enol ester, potassium cyanide (0.3 restrains, 0.005 mole) that 1.2 grams (0.005 mole) are obtained by the reaction of hydroresorcinol and 2-cyano-benzoyl chloride into.Hexaoxacyclooctadecane-6-6(0.1 gram, 0.0005 mole) and 10 milliliters of acetonitriles.At room temperature mixture was stirred 30 minutes, pour into then in 300 ml waters.Carefully the pH value is transferred to about 6 with concentrated hydrochloric acid; Use 200 milliliters of ethyl acetate extraction solution then, with 300 milliliters of saturated aqueous solution of sodium bicarbonate extractions.With concentrated hydrochloric acidization (about pH value to 3) supercarbonate extraction liquid, and with 200 milliliters of ethyl acetate extractions.Gained solution is with dried over sodium sulfate and extracting, draws 0.7 gram (theoretical yield 58%) desired product-orange-brown oil.Its structure is by infrared, nucleus magnetic resonance and mass spectrometric determination.
Embodiment 17:2-(4 '-chlorinated benzene formyl radical)-5,5-dimethyl-hydroresorcinol
Present embodiment has illustrated with the production method of metal carbonate as alkali.
With 5,5-dimethyl cyclohexane-hydroresorcinol (3.50 grams, 0.025 mole), salt of wormwood (10 gram), potassium cyanide (0.2 gram) and dimethyl formamide (40 milliliters) are put into flask together and are put into nitrogen atmosphere.Drip P-chlorinated benzene formyl chloride (3.5 milliliters, 0.025 mole).Mixture stirred 3 hours 40 ℃ the time and stirred 2 hours during at 70 ℃.
With methylene dichloride with reaction mixture dilution and with the acidifying of 3N hydrochloric acid soln.Water flushing organic phase is also used the extraction of 2.5N sodium hydroxide solution.The 3N hydrochloric acid soln acidifying of gained alkaline extraction liquid.By filter method collecting precipitation thing, water flushing and dry promptly obtains the thick product of 5.46 grams (theoretical yield 78.0%).With the high-effect liquid chromatography of HPLC() analyze, can demonstrate the 2-(4 '-chlorinated benzene formyl of 63% weight)-5,5-dimethyl-hydroresorcinol.P-chlorinated benzene formic acid is unique major impurity.
Catalyzer Solution Theoretical yield % product purity %
The KCNKCNKCNKCNKCNNaCN acetone cyanohydrin Acetonitrile acetonitrile acetonitrile 1,2-ethylene dichloride 90%1,2-ethylene dichloride 10% dimethyl formamide 1,2-ethylene dichloride acetonitrile 91.3 82.8
91.0 81.9
95.3 84.6
87.3 76.0
86.0 75.7
78.7 80.3
92.0 80.1
Test number Catalyzer Solvent Theoretical yield % Product purity %
3 KCN Ethylene dichloride 81.1 80.5
4 KCN 1, the 2-ethylene dichloride 87.5 69.9
5 Acetone cyanohydrin 1, the 2-ethylene dichloride 90.7 82.6
6 Acetone cyanohydrin Toluene 90.4 79.3

Claims (27)

1, a kind of method of producing the substituted benzoyl derivative of hydroresorcinol, the chemical formula of this derivative is as follows:
Figure 85109777_IMG1
Wherein
R 1, R 2, R 3, R 4, R 5And R 6Be respectively hydrogen or C 1-C 6Alkyl or
R 1, R 2And R 3Be
Figure 85109777_IMG2
, wherein
Ra is the C that is replaced arbitrarily by 2 to 5 methyl 1-C 4Alkyl, phenyl;
Or R wherein 1And R 2Or R 3And R 4, form C together 3-C 6Alkylene;
R 7It is halogen; Cyano group; C 1-C 4Alkyl; C 1-C 4Haloalkyl; RkS(O) n, wherein Rk is C 1-C 4Alkyl and n are 0,1 or 2; C 1-C 4Alkoxyl group or nitro;
R 8, R 9And R 10Be respectively hydrogen; Halogen; C 1-C 4Alkyl; C 1-C 4Alkoxyl group, three fluoro methoxyl groups, cyano group; Nitro; C 1-C 4Haloalkyl; C 1-C 4The alkyl sulfenyl; Phenoxy group; Or substituted phenoxy group, wherein substituting group is that halogen or halogenated methyl or both have both at the same time;
RbS(O) n, wherein n is 0,1 or 2, and Rb is C 1-C 4Alkyl, C 1-C 4Haloalkyl, phenyl or benzyl,
Figure 85109777_IMG3
, wherein Rc is C 1-C 4Alkyl,
-NRdRe, wherein Rd and Re are respectively hydrogen or C 1-C 4Alkyl;
RfS(O)-, wherein Rf is a hydrogen, C 1-C 4Alkyl, C 1-C 4Haloalkyl or C 1-C 4Alkoxyl group;
SO 2NRgRh, wherein Rg and Rh are respectively hydrogen or C 1-C 4Alkyl; Or R 8And R 9Constitute ring texture with two adjacent carbonss on the coupled phenyl ring together,
This method comprises resets corresponding enol ester in the presence of following substances:
A) with the enol ester be the cyanide source of about 1～10 molecular fraction of benchmark, this cyanide source is an alkali metal cyanide, zinc cyanide, the cyanalcohol of methyl alkyl (containing 1～4 carbon atom) ketone, benzaldehyde cyanhydrin, C 2～C 5The cyanalcohol of fatty aldehyde, three (low alkyl group) silyl prussiate or prussic acid, and with respect to the middle highly basic of 1 mole of enol ester about 1 to 4 mole (excessive), perhaps
B) with respect to the potassium cyanide of the stoichiometric quantity of enol ester or cyclic crown ether or its no ring analogues of lithium cyanide and catalytic amount.
2, production method according to claim 1, wherein cyanide source is a prussic acid.
3, production method according to claim 1, wherein cyanide source is a sodium cyanide.
4, production method according to claim 1, wherein cyanide source is a potassium cyanide.
5, production method according to claim 1, wherein cyanide source is an acetone cyanohydrin.
6, production method according to claim 1, middle highly basic wherein is tertiary amine, alkaline carbonate or alkali metal phosphate.
7, production method according to claim 1, middle highly basic wherein is trialkylamine.
8, production method according to claim 1, middle highly basic wherein is triethylamine.
9, production method according to claim 1, wherein reset to be with respect to enol ester and the cyclic crown ether of the potassium cyanide of opinion on public affairs calculated amount or lithium cyanide and catalytic amount or its no ring analogues in the presence of carry out.
10, production method according to claim 1, wherein enol ester is reacted by dione compounds and acyl halide and obtains.
11, production method according to claim 1, wherein the rearrangement of enol ester is to finish under the situation of the enol ester of not emanating out from the resultant of reaction of dione compounds and acyl halide.
CN85109777.4A 1984-12-20 1985-12-19 Process for producing acylated diketone compound Expired CN1003588B (en)

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